Oximinophosphonodithioates as insecticides and acaricides

ABSTRACT

COMPOUNDS HAVING THE FORMULA   R-C(-R&#39;&#39;)=N-O-P(=S)(-R2)-S-CH2-R3   IN WHICH R IS (1) ALKYL OR (2) LOWER ALKYLTHIOMETHYL, R1 IS ALKYL, R2 IS ALKYL, AND R3 IS (1) HYDROGEN, (2) LOWER ALKYLTHIO, (3) CYANO, (4) PHENYLTHIO, (5) SUBSTITUTED PHENYLTHIO WHEREIN THE SUBSTITUENT IS HALOGEN, (6)   -CO-NH-R4   WHEREIN R4 IS HYDROGEN OR ALKYL, (7) HALOPHENYL, (8) PHTHALIMIDO, (9) VINYL, (10) CARBOALKOXY, (11) ALKYL, (12) ETHYNYL, (13) CCL2=CR5-WHEREIN R5 IS HYDROGEN OR CHLORINE, (14)-CH2OC(O) NH (LOWER ALKYL) OR (15) BENZYLTHIO, THEIR USE AS INSECTICIDES AND ACARICIDES, PROCESS FOR PREPARING THE COMPOUNDS, INTERMEDIATES AND A PROCESS FOR PREPARING INTERMEDIATES.

United States Patent Office 3,790,670 Patented Feb. 5, 1974 3,790,670 OXIMINOPHOSPHONODITHIOATES AS INSECTI- CIDES AND ACARICIDES Arnold D Gutman, Berkeley, Calif., assignor to Staufier Chemical Company, New York, NY.

No Drawing. Original application Apr. 6, 1970, Ser. No. 26,148, now Patent No. 3,666,839. Divided and this application Mar. 9, 1972, Ser. No. 233,332

Int. Cl. A01n 91 /36 US. Cl. 424-210 20 Claims ABSTRACT OF THE DISCLOSURE Compounds having the formula in which R is (1) alkyl or (2) lower alkylthiomethyl; R is alkyl; R is alkyl; and R is (1) hydrogen, (2) lower alkylthio, (3) cyano, (4) phenylthio, (S) substituted phenylthio wherein the substituent is halogen, (6)

wherein R is hydrogen or alkyl, (7) halophenyl, (8) phthalimido, (9) vinyl, (10) carboalkoxy, (11) alkyl, (12) ethynyl, (13) CCl =CR wherein R is hydrogen or chlorine, (l4) CH OC(O)NH(lower alkyl) or (15) benzylthio, their use as insecticides and acaricides, process for preparing the compounds, intermediates and a process for preparing intermediates.

R S SCHg-R in which R is (1) alkyl having 1 to 8 carbon atoms, preferably branched chained, more preferably methyl and tbutyl or (2) lower alkylthiomethyl having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms; R is alkyl having 1 to 4 carbon atoms, preferably methyl; R is alkyl having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms and R is (1) hydrogen; (2) lower alkylthio having 1 to 4 carbon atoms; (3) cyano; (4) phenylthio; (5) substituted phenylthio wherein the substituent is halo, preferably chloro; (6) the radical wherein R is hydrogen or alkyl having 1 to 4 carbon atoms, preferably methyl; (7) halophenyl, preferably dichlorophenyl; (8) phthalimido; (9) vinyl; carboalkoxy having 1 to 5 carbon atoms; (12) ethynyl; (13) CCl =CR wherein R is hydrogen or chlorine; (l4) CH OC(O)NH(lower alkyl) or (15) benzylthio.

The compounds of the present invention can be prepared according to the following reactions: 1(

R 2 1 I (b) R S SCHgR R R2 R1 in which, R, R R and R are as defined.

In the event that the desired compound cannot be prepared because of difiiculty of preparing or obtaining the compound HSCH R of reaction I(b), then the following reaction can be utilized to obtain the compounds of this in which R, R R and R are as defined and X is chlorine, bromine, or iodine. The compound recited in reaction 1(a), and I(b) when R is lower alkylthiomethyl having 1 to 4 carbon atoms and R is alkyl having 1 to 4 carbon atoms, if not obtainable can be prepared according to the following reaction:

Preferably, reaction 1(a) is carried out by reacting preferably equal mole amounts of the two reactants. If an excess of either reactant is used, the reaction still proceeds but yields are reduced. The reactants can be combined in any desired manner but preferably, the reaction is run in a solvent such as THF by first-preparing the salt of the oxime reactant with an acid acceptor such as potassium t-butoxide at room temperature and then preferably, slowly adding the dichloride reactant thereto, preferably in solution with a solvent, for example, THF, at a temperature below about 15 C. for control. However, the oxime reactant can be used in place of the salt, preferably in the presence of the acid acceptor. The resulting product is recovered and purified by standard procedure. For example, the resulting product can be recovered from the reaction mixture and purified from the reaction mixture by adding the mixture to a non-polar solvent such as benzene. The benzene mixture is then washed with water,

dilute NaOH solution and then again by water. The hen-- zene is evaporated after the water has been removed, for example, by treatment with anhydrous MgSO to yield the purified product.

Reaction I(b) is carried out by reacting preferably equal mole amounts of the two reactants. If an excess of either reactant is used, the reaction still proceeds but yields are reduced. The reactants can be combined in any manner but preferably the phosphorus-containing reactant is slowly added to the reactant containing the -SH group in a solvent such as THF, preferably with stirring. More preferably, an alkali metal salt of this reactant is used to reduce the chance of a violent reaction. The temperature of the reaction is not critical, however, better yields are obtained by heating the reactants at reflux for a time suflicient to allow completion of the reaction. The resulting product can be recovered from the reaction mixture and purified by standard procedures. For example, the desired reaction product can be recovered from the reaction mixture by adding the mixture to a nonpolar solvent such as benzene. The benzene mixture is then washed with water, dilute NaOH solution and then again by water. The benzene is evaporated after the water has been removed, for example, by treatment with anhydrous MgSO, to yield the purified product.

The process of this invention is represented by reaction II(a) and gives intermediate compounds useful to prepare the compounds of this invention. In other words, the process of this invention is a process for preparing a compound having the formula in which R, R and R are as defined comprising reacting a compound of the formula in which R and R are as defined with a compound of the formula in which R is as defined.

The process of this invention is carried out by merely reacting preferably, about 2 moles of the oxime reactant with preferably about one mole of the thionophosphine sulfide reactant. If different proportions of either reactant are used, the reaction still proceeds but yields are lowered. The reactants can be combined in any desired manner. The reaction readily proceeds at room temperature and preferably is run under anhydrous conditions in a common solvent for the reactants such as benzene. The dithiophosphonic acid product can be recovered from its solvents in pure form, but it is preferred not to do so. If prolonged storage of the compound is desired, it is preferable to prepare either the alkali, alkaline or heavy metal salt of the acid.

Another process of this invention is represented by reaction II(b) which utilizes as a reactant the product of reaction II(a) preferably as a solution in the solvent utilized for reaction II( a) In this process, the reaction is carried out by reacting preferably about equal mole amounts of the reactants. If an excess of either reactant is used, the reaction -still proceeds but again yields are lowered. Although the reactants can be combined in any desired manner, it is preferred to add the halide reactant to a solution of the dithiophosphonic acid reactan preferably the acid is not recoveredfrom the solvent in which it is prepared. Preferably, the reaction is carried out at below room temperature about 1020' C. for control and in the presence of a base, such as triethyl amine, to take up the liberated acid reaction product. The reaction product is recovered by conventional means such as described for reaction ([(b).

Preferably, reaction {II(a) is carried out by preparing and adding chloro-Z propanone to a solution of an excess of the mercaptan reactant in the presence of an HCl acceptor at such a rate that the temperature does not exceed about 30 C. Thereafter, the mixture is heated to about 45 C. with stirring until the reaction is complete. The product is recovered by conventional techniques.

Preferably, reaction III(b) is carried out by merely stirring at near room temperature for about 1 hour a mixture of about equal amounts of the two reactants dissolved in 10% ethanol solution after an aqueous solution of a base, such as sodium carbonate in water which had been slowly added over a period of about 20 minutes. The product is again recovered by conventional techniques.

The novel intermediate compounds of this invention which are (l) useful in preparing the compounds of this invention, for example, by reaction II(b), heretofore described or (2) as insecticides or acaricides, are those having the formula R S SE c=N0f R1 in in which R is (1) alkyl having 1 to 8 carbon atoms, preferably branched chained, more preferably methyl and tbutyl or (2) lower alkylthiomethyl having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms; R is alkyl having 1 to 4 carbon atoms, preferably methyl and R is alkyl having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms.

These intermediate compounds are preparable according to reaction II(a) and the subsequent discussion thereof.

If desired, the alkali, alkaline earth or heavy metal salts of the intermediate acid compounds can be prepared by convention techniques such as by reacting the acid with a base. The salts will either be mono, di or tri basic depending upon the valency of the metal atom used to form the salt.

Preparation of the compounds of this invention, the process 'for preparing intermediates and the intermediates are illustrated in the following examples.

EXAMPLE I CH3 S SE 0- aeetoneoximino ethyl-dithiophosphonic acid EXAMPLE H CH3 S S-CH3 CH C2115 O- (acetoneoximino) ethyl-S-methylphosphonothioate 24.8 grams (0.1 mole) of ethylthionophosphine sulfide is combined with 200 ml. of anhydrous dioxane in a 600 m1. beaker. The mixture is magnetically stirred at room temperature and 22.0 grams (0.3 mole) of acetoneoxime is added and the resulting mixture is stirred for 30 minutes until a clear solution containing the compound of Example I is obtained.

The solution is cooled in an ice bath to C., and 42.5 grams (0.3 mole) of methyliodide is added, followed by the addition of 30.3 grams (0.3 mole) of triethylamine over a period of 10 minutes, so that the temperature of the reaction does not exceed C. The rsulting mixture is stirred at room temperature for one hour, then poured into 500 ml. of benzene. The benzene mixture is washed with 200 ml. of H 0, 100 ml. of saturated NaHCO solution followed by two 100 ml. portions of H 0. The benzene phase is dried with anhydrous MgSO and evaporated under reduced pressure to yield 40.8 grams (99% of theory) of the desired compound. N =l.5500. The structure is confirmed by IR and NMR.

EXAMPLE III 0 Has CH;

G=NOH Methyl mercapto-2-propanoneoximine This example teaches the synthesis of the alkylthioketoxime useful in the preparation of the compounds of this invention.

202 grams (2.0 moles) of triethylamine and 300 ml. of acetone are combined in a liter three-neck flask equipped with a condenser, stirrer, thermometer and dropping funnel. An excess of methylmercaptan is bubbled into the stirring solution at room temperature. To the resulting mixture is added 185 grams (2.0 moles) of chloro2-propanone at such a rate that the temperature does not exceed 30 C. After the addition is completed, the mixture is stirred and heated to 45 C. for 15 minutes. The mixture is cooled, poured into 500 ml. of benzene, and washed with two 300 ml. portions of water. The benzene phase is dried with anhydrous MgSO and evaporated to yield 165.5 grams (81% of theory) of methylmercapto-Z-propanone. N "=1.4780.

104 grams (1.0 mole) of the methylmercapto-Z-propanone, 83.5 grams (1.2 moles) of hydroxylamine hydrochloride, 400 m1. of water and ml. of ethanol are combined in a 1 liter three-neck flask equipped with a stirrer, thermometer and dropping funnel. The mixture is stirred at room temperature, and a solution of 62 grams (0.5 mole) of sodium carbonate monohydrate in 150 ml. of H 0 is added over a period of 30 minutes. The resulting mixture is stirred at room temperature for one hour and then poured into 1 liter of benzene. The benzene phase is separated, dried with anhydrous MgSO and evaporated to yield 98 grams (82.3% of theory) of methylmercapto- 2-propanoneoxime. N =1.5 190.

EXAMPLE IV CH S OH: S S CH S OH:

C=N O P CH CzHa 0-(methylthioaeetoneoximino) ethyl-2-( met hylthlomethyl )phosphonodithioate 12.4 grams (0.05 mole) of ethylthiophosphine sulfide, 11.9 grams (0.1 mole) of methylmercapto-2-propanoneoxime of Example I and 200 m1. of dioxane are combined in a 1 liter beaker and stirred magnetically at room temperature until a solution is obtained. The solution is stirred and cooled to 10 C. in an ice bath. 9.7 grams (0.1 mole) of chloromethylmethylsulfide is added. Next, 15.1 grams (0.15 moles) of triethylamine is added over a period of 10 minutes. The resulting mixture is stirred at room temperature for 1 hour, then poured into 500 ml. of benzene and consecutively is washed with 200 ml. of water, 100 ml. of saturated sodium bicarbonate solution and two 100 ml. portions of water. The benzene phase is dried with anhydrous MgSO and evaporated to yield 27 grams (89% of theory) of the desired compound. N =1.5937.

The following is a table of certain selected compounds that are preparable according to the procedure described hereto. Compound numbers are assigned to each compound and are used throughout the remainder of the application.

TABLE I R\ fi/SCHzR C=NOP Compound M.P., C. No. or N13 R R R R 1 .z': Semi-solid (OH )gCHCHa CH3 02H; -CNHCH5 1.5840 CH! CH: C1H5 -SCH 62-66 CH; CHI CgHs (I) '(NH1 4..:-.==:: 1.5923 CH CH 02H; 0

O 5...:22: 1.5978 CH3 CH 01H! S Cl 1.5356 CH: CH3 CzHs CH=CC11 1.5507 CH CH5 C2115 -CEN 1.6043 CH; CHz C2115 SQ 9-.::;-.:: 1.5536 CH: CH; C2115 -C:ECH 10.....-:.':::: 1.5845 CH; CH; C2H5 TABLE I-Contlnued Cornpound M.P., C.

0. or N R R R R 11 1. 5872 CH3 CH3 (4H5 '1 12 1. 5552 CH3 CH C2115 -C1=C C1:

1. 5420 CH3 CH3 CzH CHOC (O) NHCH; 1. 5712 CHaS CH: CH3 C1115 H 1. 5937 0113501311 CH3 C H5 SCH3 1. 5640 CHQOHI H3 C2115 SCH3 1. 5885 CHQSCHQ CH3 C2115 '-CH=CC13 1. 5038 CH3 CH3 CQHQ -C OCzHs 19 1. 5946 CHZCH: CH3 03H;

- S C H1 1. 6043 CHaCH: CH3 02B; S G

1. 5550 CHZCHQ CH3 C711 SC1H5 1. 5518 CH3 CH3 0755 S (EH5 1. 5597 CHI CH3 CzHk -CNHCH 1. 5574 CHaCHg CH3 02H; C E CH 1. 5472 2H5 CH3 62H --0 E N 1. 5435 C2115 02H; CzHg C N 1. 5400 3H7 CH3 CgH5 C E N I 1. 5770 C2115 02H; 01H; SCH3 1. 5200 CH CH; 2115 OHflC-E(CH3)Q 1. 5488 C3H7 CH3 0311;, C 011 1. 5714 C2115 CH C2115 -SCH(CH:4)1 1. 5555 CH3 CH3 C2115 H 1. 5480 CH3 CH3 C1115 SCH(CH3)1 1. 5684 021158 CH5 CH3 0 115 C E N 1. 5757 CzH S CH1 CH3 C3H5 --C N 1. 5975 (EH53 CH: CH C2115 -S CH 1. 5805 CLHsSCHg CH; C2115 -503H5 1. 5714 CzHaS CH; CH; C2115 -H 1. 5502 CH3 CH3 C2115 CH=CH 1. 5412 02H; CH3 01H; CH=C H: 1. 5480 (CH3)2CH CH3 C2115 -C 5 CH 1. 5383 (OH3)2CH- CH3 C1H5 C N 1. 5734 (C 312CH- CH 02H; 5 CH 1. 5557 CHsCHg CH3 C5H5 H 1. 5427 02115 01H; C2115 -H 1. 5465 CaH1 CH CzHg H 1. 5430 (CH3)3U- CH4 C2115 C CH 1. 5310 (CH3) C C113 C2115 C'=N 1. 5492 CH3)aC- CH C1115 --SC H5 1. 5612 (OH C- CH3 61115 --S CH3 1. 5318 (CH3)3C- CH3 03115 g 1. 5377 (CH3)3C CH; C9115 1. 5327 (CHahCH- (CHQ CH CzH 1. 5538 (CH3) CH (CH:)3CH C2115 1. 5330 (CH3)5CH (OH3)2CH C2H5 1.5268 (CHQgCCHg CH3 2H5 1. 5260 (CH3)3CCH7 CH3 C2115 1. 5376 (C H3 3CCH1 CH C2H5 1. 5075 (C H3) CCH7 CH CgH l. 5300 (CH3)3C CH3 C7H5 l. 5275 (CHahCHCH; CH: B B 1. 5485 (CHahCHCH; CH3 ca fi 1. 5447 (CH3): CHCH, CH3 Calls 1. 5290 (CHQ OHCH; CH3 02H; 1. 5333 (CH3)2CHCHI CH3 C111 1. 5503 (CHghCHCHg CH3 02H& 1. 5643 CH3 CH3 CH3 I Compound No. 2 prepared in Example II. Compound No. 15 prepared in Example IV.

The following tests illustrate utility of the compounds The following insect species were used in evaluation tests for insecticidal activity (l) Housefiy (HF)-Musca domestica (Linn.).

(2) German Roach (GR)-Blalella germanica (Linn). (3) Salt-Marsh Caterpillar (SMC)-Estigmene acrea (4) Lygus Bug (LB)Lygus hesperus (Knight).

(5) Bean Aphid (BA)--Aphis fabae (Scop.).

The Housefly (HF) was used in evaluation tests of selected compounds as insecticides by the following procedure. A stock solution containing 100 ,ug/ml. of the toxicant in an appropriate solvent was prepared. Aliquots of this solution were combined with 1 milliliter of an acetone-peanut oil solution in an aluminum dish and allowed to dry. The aliquots were there to achieve desired toxicant concentration ranging from 100 g. per dish to that at which 50% mortality was attained. The dishes were placed in a circular cardboard cage, closed on the bottom with cellophane and covered on top with cloth netting.

Twenty-five female houseflies, three to five days old, were introduced into the cage and the percent mortality was recorded after 48 hours. The LD values are expressed in terms of ,ug. per 25 female flies. The results of these insecticidal evaluation tests are given in Table [I under HF.

In the German Cockroach (GR) tests, 10 one-month old nymphs were placed in separate circular cardboard cages sealed on one end with cellophane and covered by a cloth netting on the other. Aliquots of the toxicants, dissolved in an appropriate solvent, were diluted in water containing 0.002% of a wetting agent, Sponto 22l (a polyoxyether of alkylated phenols blended with organic sul fonates). Test concentrations ranged from 0.1% downward to that at which 50% mortality was obtained. Each of the aqueous suspensions of the candidate compounds was sprayed onto the insects through the cloth netting by means of a hand-spray gun. Percent mortality in each case was recorded after 72 hours, and the LD values, expressed as percent of toxicant in the aqueous spray, were recorded. These values are reported under the column GR in Table II.

For testing the salt marsh caterpillar, test solutions were prepared in an identical manner and at concentrations the same as for the German cockroach above. Sections of bitter dock (Rumex obtusifolus) leaves, l-1.5 inches in length were immersed in the test solutions for 10 to 15 seconds and placed on a wire screen to dry. The dried leaf was placed on a moistened piece of filter paper in a Petri dish and infested with -3rd instar larvae. Mortality of the larvae was recorded after 72 hours and the LD values are expressed as percent active ingredient in the aqueous suspension.

The lygus bug (LB) Lygus hesperus was tested similarly as the German cockroach. The caged insects were sprayed with the candidate compounds at concentrations ranging from 0.05% downward to that at which 50% mortality was obtained. After twenty-four and seventytwo hours, counts were made to determine living and dead insects. The LD (percent) values were calculated. These values are reported under the column LB in Table II.

The insect species black bean aphid (BA) Aphis fabae (Scop.) was also employed in the test for insecticidal activity. Young nasturtium (Tropaeolum sp.) plants, approximately 2 to 3 inches tall, were used as the host plants for the bean aphid. The host plant was infested with approximately 50-75 of the aphids. The test chemical was dissolved in acetone, added to water which contained a small amount of Sponto 221, an emulsifying agent. The solution was applied as a spray to the infested plants. Concentrations ranged from 0.05 percent downward until an LD value was achieved. These results are given in Table II under the column BA.

10 ACARICIDAL EVALUTION TEST The two-spotted mite (2SM), Tetranychus urticae (Koch), was employed in tests for miticides. Young pinto bean plants or lima bean plants (Phaseolus sp.) in the primary leaf stage were used as the host plants. The young pinto bean plants were infested with about mites of various ages. Dispersions of candidate materials were prepared by dissolving 0.1 gram in 10 ml. of a suitable solvent, usually acetone. Aliquots of the toxicant solutions were suspended in water containing 0.002% v./v. Sponto 22l, polyoxyethylene ether sorbitan monolaurate, an emulsifying agent, the amount of water being sufficient to give concentrations of active ingredient ranging from 0.05% to that at which 50% mortality was obtained. The test suspensions were then sprayed on the infested plants to the point of run off. After seven days, mortalities of post-embryonic and ovieidal forms were determined. The percentage of kill was determined by comparison with control plants which had not been sprayed with the candidate compounds. The LD values was calculated using wellknown procedures. These values are reported under the columns 2SM-PE and 2SM-Eggs in Table II.

SYSTEMIC EVALUATION TEST This test evaluates the root absorption and upward translocation of the candidate systemic compound. The twospotted mite (25M), T etranychus urticae (Koch) and the bean aphid (BA), Aphis fabae (Scop.) were employed in the test for systemic activity.

Young pinto bean plants in the primary leaf stage were used as host plants for the two-spotted mite. The pinto bean plants were placed in bottles containing 200 ml. of the test solution and held in place with cotton plugs. Only the roots were immersed. The test solutions were prepared by dissolving the compounds to be tested in a suitable solvent, usually acetone, and then diluting with distilled water. The final acetone concentration never exceeded about 1 percent. The toxicants were initially tested at a. concentration of 10 parts per million (p.p.m.). Immediately after the host plant was placed in the test solution it was infested with the test species. Mortalities were determined after seven days.

Young nasturtium plants were used as the host plants for the bean aphid. The host plants were transplanted into one pound of soil that had been treated with the candidate compound. Immediately after planting in the treated soil the plants were infested with the aphids. Concentrations of toxicant in the soil ranged from 10 p.p.m. per pound of soil downward until an LD value was obtained. Mortality was recorded after 72 hours.

The percentage of kill of each test species was determined by comparison with control plants placed in distilled water or untreated soil. The LD values were calculated. These systemic test results are reported in Table II under the columns BA-sys and ZSM-sys.

TABLE II.-LD50 VALUES Two-spotted mites Percent Percent Compound HF, BS-SYS, SYS, number: pg. GR LB SMC BA p.p.m. PE Eggs p.p.m.

TABLE II-Continued Two-spotted. mites Percent Percent Compound HF, BS-SYS, SYS number: g. GR LB SMC p.p.m. PE Eggs ppm,

1 Compound prepared in Example I.

As those in the art are well aware, various techniques are available for incorporating'the active component or toxicant in. suitable pesticidal compositions. Thus, the pesticidal compositions can be conveniently prepared in the form of liquids or solids, the latter preferably as homogeneous free-flowing dusts commonly formulated by admixing the active component with finely divided solids or carriers as exemplified by talc, natural clays, diatomaceous earth, various flours such as walnut shell, wheat, soya bean, cottonseed and so forth.

Liquid compositions are also useful and normally comprise a dispersion of the toxicant in a liquid media, although it may be convenient to dissolve the toxicant directly in a solvent such as kerosene, fuel oil, xylene, alkylatednaphthalenes or the like and use such organic solutions directly. However, the more common procedure is to employ dispersions of the toxicant in an aqueous media and such compositions may be produced by forming a concentrated solution of the toxicant in a suitable organic solvent followed by dispersion in water, usually with the aid of surface active agents. The latter, which may be the anionic, cationic, or monionic types, are exemplified by sodium stearate, potassium oleate and other alkaline metal soaps and detergents such as sodium lauryl sulfate, sodium naphthalene sulfonate, sodium alkyl naphthalene, sulfonate, methyl cellulose, fatty alcohol ethers, polyglycol fatty acid esters and other polyoxyethylene surface active agents. The proportion of these agents commonly comprises l-l5% by weight of the pesticidal compositions although the proportion is not critical and may be varied to suit any particular situation.

I claim:

1. A method of controlling insects comprising applying thereto an insecticidally efl'ective amount of a compound having the formula S SCHr-R' I! in which R is (1) alkyl having 1 to 8 carbon atoms, or (2) lower alkylthiomethyl having 1 to 4 carbon atoms;

R is alkyl having 1 to 4 carbon atoms;

R is alkyl having 1 to 4 carbon atoms;

R is (1) hydrogen; (2) lower alkylthio having 1 to 4 carbon atoms; (3) cyano; (4) phenylthio; (5) substituted phenylthio wherein the substituent is halo, (6) the radical 0 -ii-NHR wherein R is hydrogen or alkyl having 1 to 4 carbon atoms, (7) halophenyl; (8) benzylthio; (9) vinyl; (10) carbalkoxy having 1 to 4 carbon atoms; (11) alkyl having 1 to 5 carbon atoms; (12) ethynyl; (13) CCl=CR wherein R is hydrogen or. chlorine; or (14) CH OC(O)NH(lower alkyl). 2. The method of claim 1 in which R is alkyl having 1 to 4 carbon atoms, R is methyl, R is alkyl having 1 to 2 carbon atoms, and R is ethylthio.

3. The method of claim 1 in which R is alkyl having 1 to 4 carbon atoms, R is methyl, R is alkyl having 1 to 2 carbon atoms, and R is methylthio.

4. The method of claim 1 in which R is alkyl having 1 to 4 carbon atoms, R is methyl, R is alkyl having 1 l to 2 carbon atoms, and R is ethynyl.

5. The method of claim 1 in which R is alkyl having 1 to 4 carbon atoms, R is methyl, R is alkyl having 1 to 2 carbon atoms, and R is ethynyl.

6. The method of claim 2 in which R is methyl, R is methyl, R is ethyl and R is ethylthio.

7. The method of claim 4 in which R is ethyl, A is methyl, R is ethyl, and R is cyano.

8. The method of claim 4 in which R is propyl, R is methyl, R is ethyl, and R is cyano.

9. The method of claim 5 in which R is methyl, R is methyl, R is ethyl and R is ethynyl.

10. The method of claim 5 in which R is sec-butyl, R is methyl, R is ethyl and R is ethynyl.

11. A method of controlling acarids comprising applying thereto an acaricidally effective amount of a compound halving the formula:

S SCHz-R in which R is (1) alkyl having 1 to 8 carbon atoms, or (2) lower alkylthiomethyl having 1 to 4 carbon atoms;

R is alkyl having 1 to 4 carbon atoms;

R is alkyl having 1 to 4 carbon atoms;

R is (1) hydrogen; (2) loweralkylthio having 1 to 4 carbon atoms; (3) cyano; (4) phenylthio; (5) substituted phenylthio wherein the substituent is halo; (6) the radical R 3-NHR wherein R is hydrogen or alkyl having 1 to 4 can carbon atoms, (7) halophenyl; (8) benzylthio; (9) vinyl; (10) carbalkoxy having 1 to 4 carbon atoms;

14 (11) alkyl having 1 to 5 carbon atoms; (12) ethynyl; (13) CClg=CR wherein R is hydrogen or ch10- rine; or (14) --CH OC(O)NH(lower alkyl).

12. The method of claim 11 in which R is alkyl having 1 to 4 carbon atoms, R is methyl, R is alkyl having 1 to 2 carbon atoms, and R is ethylthio.

13. The method of claim 11 in which R is alkyl having 1 to 4 carbon atoms, R is methyl, R is alkyl having 1 to 2 carbon atoms, and R is methylthio.

14. The method of claim 11 in which R is alkyl having 1 to 4 carbon atoms, R is methyl, R is alkyl having 1 to 2 carbon atoms, and R is cyano.

15. The method of claim 11 in which R is alkyl having 1 to 4 carbon atoms, R is methyl, R is alkyl having 1 to 2 carbon atoms, and R is ethynyl.

16. The method of claim 12 in which R is methyl, R is methyl, R is ethyl and R is ethylthio.

17. The method of claim 14 in which R is ethyl, R is methyl, R is ethyl, and R is cyano.

18. The method of claim 14 in which R is propyl, R is methyl, R is ethyl, and R is cyano.

19. The method of claim 15 in which R is methyl, R is methyl, R is ethyl and R i s ethynyl.

20. The method of claim 15 in which R is sec-butyl, R is methyl, R is ethyl and R is ethynyl.

References Cited UNITED STATES PATENTS 3,666,839 5/1972 Gutman 260-940 2,816,128 12/1957 Allen 260-944 X 2,957,016 10/ 1960 Diamond 260944 X SAM ROSEN, Primary Examiner V. D. TURNER, Assistant Examiner US. Cl. X.R. 424200, 211 

